Apparatus for contacting gases with granular solids



July 4, 1950 s. c. EAs-rwoop Erm. 2,513,995

lPFRA'IUS FOR CONTACTING GASES WITH GRANULAR SOLIDS AGE/V7' 0194770 NE'Y July 4, 1950 s. c. EASTwooD Erm. 2,513,995

APPARATUS FOR coNTAcTING GASES WITH GRANULAR soLIns Filed Jan. 27. 1948 2 sheets-sheet 2 STEAM INVENTOR. SY/ V/VDE/ 6I EAST WOOD Y and HOHER T D. DRE W Wma/ 7 AGENT 0R ATT IIPNEY Patented July 4, 1950 APPARATUS FOR CONTACTING GASES WITH GRANULAR SOLIDS Sylvander C. Eastwood, Woodbury, and Robert D.

Drew, Wenonah, N. J., assignors to Socony- Vacuum Oil Company, Incorporated, a corporation of New York Original application August 2, i946, Serial No. 687,902. Divided and this application January 27, 1948, Serial No. 4,564

6 Claims.

This invention relates to a process for conductingfchemical reactions and to apparatus for practising the novel process. Particularly, the invention-relates to method and means for inducing desired temperature changes in vapor phase reactants for conducting chemical reactions` at high temperatures for short reaction periods.

The invention is peculiarly suited to endothermic reactions, particularly those consuming large amounts of heat. A typical reaction is the conversion of higher boiling hydrocarbons to low boiling olens by reaction for very short reaction times at elevated temperatures, usually above about 1400 F. For example, crude petroleum or gas oil is readily converted to ethylene with yields in the order of 30 per cent by weight by thermal cracking at about 15G0 F. for 0.2 second. Lighter' hydrocarbons require higher temperatures, for example, propane is best cracked at '1600 F. or above While ethane requires temperatures on the order of 1700 to 1800 F. to obtain good conversions to ethylene.

In any event, the reaction time must be maintained very short in order to avoid secondary reactions such as condensation to aromatic hydrocarbons.` These reactions are extremely difcult to conduct in conventional tube furnaces since the heat transfer rates are relatively low and excessive coke deposits are rapidly built up.

Accordingk to the present invention, the charge is rapidly heated to the desired temperature by direct Contact with a highly heated granular solid and is then rapidly cooled to temperatures which will inhibit further reaction by contact with a relatively' cold solid of the same general nature. The invention provides the relatively hot and relatively cold beds of granular solid as superimposed layers in a single contacting zone. The upper layer is relatively cold solid which rapidly quenches the reaction products and is thereby itself rapidly heated to a temperature approaching the desired reaction temperature. The granular solid moves downwardly through thisL (Cl. 22S- 284) from the bottom of the Acontacting zone and recycled inthe system.

As a preferred embodiment, the additional input of heat to malte up for that lost by reason of the endothermic nature of the reaction is supplied by a portion of the granular solid heat transfer materia-l circulated through the system. According to this embodiment, one portion of the granular solid is supplied to the top of the contacting zone at a temperature suiiiciently below the reaction temperature that it will quench the reaction products to the desired degrec. The remainder of the granular solid is heated to a temperature not lower than that at which the reaction is to be conducted and is then"L supplied to an intermediate portion of the contacting Zone as the source of additional heat input. Other suitable methods of adding additional heat include heat transfer coils and hot inert gases, for example highly heated steam and products of combustion introduced directly to the contacting zone.

Two forms of apparatus for practising the preferred embodiment of the invention are shown in the annexed drawings; wherein Figure 1 is a diagrammatic showing of suitable apparatus and includes a cross section of the reactor showing internal construction of this element; l

Figure 2 is a vertical section through a vessel which includes both a heater and a reaction section; and

Figure 3 is a detail view in partial section of a tube for supplying hot granular solid to an intermediate point in the contacting bed.

Referring specifically now to Figure l, a granular solid heat transfer material is circulated in a closed cycle including a reactor I0, an elevator ll, a heater l2, and a cooler I3. Granular solid is discharged from the top of elevator ll' to a feed chute 8 having a classifier lli for removal of particles smaller than that desired in the system. The feed chute 3 is divided at 9 to split the stream and divert a portion thereof to the heater l2 and another portion to the cooler 1 3. For this purpose the feed chute 8 should be flat bottomed in order that the classication of granular solids in the chute shall not result in a difference in size distribution in the streams diverted to heater I2 and cooler I3. The division of the stream is made on a vertical plane at lll thus giving the same size distribution in the two streams.

The solids passing downwardly through cooler i3 as a substantially compact moving bedare cooled therein as by passing therethrough a blast of air from compressor I5. This air is heated in cooler I3 and is then transferred by pipe I6 to a line supplying preheated air to heater I2. To maintain a desired degree of preheat on the air supplied to heater I2, a portion of the air from compressor I5 ,may be passed through a line burner I1 wherein a small amount of fuel is burned and the effluent is then mixed with the air from pipe I6 and the mixture supplied to heater I2. Gaseous fuel is admitted to heater I2 by inlet port I8 and combustion of this fuel in the preheated air raises the temperature of the granular solids passing downwardly through heater I2 as a substantially compact moving bed, flue gases being removed by line I 9 to a stack or suitable economizer. As shown, the solids from heater I2 and cooler I3 are purged with an inert gas, such as steam, admitted at 20 and 20 to insure that combustion supporting gases are not transferred to the reactor.

In the upper portion of the reactor are two bulk supply zones provided by plates 2I and 22. The cold solid from cooler I3 is admitted to the top supply zone above plate 2I while the hot solid from heater I2 is introduced to the lower supply zone between plates 2l and 22. Granular solid supply tubes depend from each of the plates 2l and 22 to supply the granular solid to the desired points in the reaction Zone. Cold feed tubes 23 extend downwardly through the lower bulk supply zone to a point below plate 22 where they discharge onto the top of a substantially compact bed of moving solids. Hot supply tubes 24 extend downwardly from the plate 22 to a still lower point in the reactor to introduce the hot -granular solid to an intermediate point in the moving bed. At a point still further down, a suitable reactant is introduced, for example, a mixture of oil and water to be vaporized for cracking the oil to give large yields of ethylene. This introduction may be by means of any suitable fluid distributer, such as the inverted angles shown diagrammatically at 25.

Below the reaction zone are a series of flow control plates 26, 21 and 28 which act to induce uniformity of ow across the reactor. Purging steam may beadmitted at inlet port 29 below the upper flow :control plate 26. The granular solid is then transferred by conduit 30 having a depressuring pot 3I and a Valve 32 to the elevator I I for recirculation in the system.

In a typical operation for the cracking of gas oil in the presence of per cent by weight of steam, the apparatus is operated to give a reaction temperature of l550 F. and a reaction time of 0.2 second. The oil and water are introduced in liquid phase to be evaporated by the residual heat contained in the granular solid heat transfer material giving an outlet temperature to the elevator of 980 F. Granular solid at this temperature is divided to pass about ve parts by weight of the solid through heater I2 and two parts by weight through the cooler I3. The solid is heated in heater I2 to 1600 F. and transferred at that temperature to the reactor. About half the air for the heater I2 is passed through the solids in cooler I3 and is thereby heated to 980 F. and mixed with the other half of the air at 100 F. giving an air stream which will form combustible mixtures with the fuel gas at temperatures below that at which ignition takes place in the burners and supply lines. drawn at outlet port 33 at about 600 F. and is passed to suitable puricationequipment for separation of the valuable components thereof.

A gaseous product mixture is with-| 'Ihe apparatus of Figure 2 is generally similar to that of Figure 1 except that no separate cooler is provided and the heating zone is enclosed by the same vessel 34 which contains the reaction zone. Use of this apparatus preferably includes a lower recirculation temperature and this is achieved by cooling the granular solid leaving the bottom of vessel 34 as hereinafter described. Relatively cool granular solid is admitted to the top of vessel 34 from feed pipe 35 to fall onto a plate 36. Steam admitted at 31 serves to seal this bulk supply zone against the admission of air. A number of feed pipes depend from plate 36 and a portion thereof designated .by reference character 38 supply relatively cool solid directly to the top of the moving bed in the reaction zone. The remaining feed pipes 39 supply granular solid to the top of a moving bed in a heating zone to which air and fuel are supplied as by inverted ang-les 40. The flue gas is discharged at outlet port 4I. Feed pipes 42 extend downwardly to an intermediate point in the reaction zone to supply hot solids from the heating zone. The heating and reaction zones are effectively isolated by steam or other inert gas pressure supplied at inlet 31 mentioned above and at the inverted angles 43 in the bottom of the heatingI zone. Oil and water, or if desired oil vapors and steam, are supplied at inverted angles 44 to the reaction zone and are treated in much the same manner.

Preferably, the -granular solid withdrawn from the reaction chamber in apparatus of this type is cooled as by a water spray admitted through manifold 45 and branch pipes 46. Vaporization of this water provides purging steam below the flow control plate 26. If it is desired to cool to an extent greater than can be tolerated by the amount of purging steam needed in the bottom of the :chamber additional cooling may take place in asaseparate chamber below the contacting vessel Since the several feed tubes for granular solid pass through zones of differing temperature, they can be insulated as shown in Figure 3 wherein a supply pipe 42 is fitted with a concentric outer pipe 41 with insulation 48 therebetween. The bottom ends of the pipes supplying hot granular solid to intermediate points in the contacting bed are preferably fitted with flared skirts 49 which act as baiiles to provide an open space below the ends of the tubes and thus give the proper ratio between the flow rates from pipes 38 and pipes 42. It is desirable that the flared skirts have orifices therethrough to permit the flow of gases and thus minimize reduction of the eifective gas passage at this point. One manner of accomplishing this result is shown in Figure 3 wherein the flared skirts are louvered as indicated at 50.

This application is a division of our copending application Serial No. 681,902, filed August 2, 1946.

We claim:

1. Apparatus for conducting a chemical reaction comprising in combination, a reaction vessel, a heater for solid granular material, a, cooler for solid granular material, an upper horizontal partition across said reaction vessel spaced below the upper end thereof, a second horizontal partition across said reaction vessel spaced substantially below said rst partition and a substantial distance above the lower end of said vessel, said partitions dividing said reaction vessel into three superposed chambers, a confined passage for solid material transfer communicating said cooler with the chamber above said Latrasos upper partition., a confined'. passage for solid material transfer communicating.' said heater with the chamber between said partitions', a plurality of tubes extending down from said upper partition to a level in said reaction vessel below said second partition, a second plurality of tubes extending downwardly from said second partition to' a level in: said vessel spaced a substantial distance below the klower ends of said iirst named tubes, fluid distributors in said vessel a substantial distance below the lower ends' of said second named tubes, a gas outlet from said vessel at a level below saidA lower partition and above the lower ends of said iirstnarned tubes, and an outlet conduit for solid material con nected to the lower end of said reaction vessel.

2. Apparatus for conducting a chemical reaction comprising incombination, a reaction vessel, a heater for 'solid granular material positioned above said reaction vessel, a cooler for sol-id granular material also positioned above saidireactio'n' vessel, an upper horizontal partition across said' reaction vessel spaced below the upper end thereof, a second horizontal partition across said reaction vessel spaced substanm tially below said first partition and a substantial distance above the lower end of said vessel, said partitions dividing said reaction vessel into three superposed chambers, a conduit for solid flow extending downwardly fromrsaid cooler to the chamber above said upper partition, a conduit for solid flow extending down from said heater to a point in the upper portion'of the chamber between said two partitions, a plurality of tubes for solid flow extending from the upper face of f said upper partition to points in said reaction vessel shortly below said lower partition, a plurality of tubes for solid flow extending. from the upper surface of said lower partition to points in said reaction vessel spaced a substantial vertical distance below the lower ends of said first named tubes, fluid distributors in said reaction vessel spaced a substantial distance below the lower ends of said second named tubes, a conduit means to supply iiuid to said distributors, a gas outlet on said vessel at a level between said lower partition and the lower ends of said rst named tubes, an outlet conduit for solid withdrawal connected to the lower section of' said reaction Vessel, a conveyor for transferring solid material from said outlet conduit to a discharge at a level above said heater and cooler and conduits communicating the conveyor discharge with the upper sections of both the heater and the cooler.

3. Apparatus for conducting a chemical reaction comprising in combination, a reaction vessel, a heating vessel for heating solid granular material positioned above said reaction vessel, an inlet for a heating fluid connected near one end of said heating vessel and an outlet for used heating fluid near the opposite end of said heater, a cooling vessel for cooling solid granular material, a cooling fluid inlet near one end of said cooling vessel and a cooling fluid outlet near the opposite end thereof, an upper horizontal partition across said reaction vessel spaced below the upper end thereof, a second horizontal partition across said reaction vessel at a level in the up-per section thereof spaced substantially below said rst partition, said partitions dividing said reaction vessel into three superposed chambers, a confined passage for solid material transfer communicating said cooling vessel with the chamber above said upper partition, a confined passage for solid material transfer communicating said heating vessel with the chamber between said partitions', a plurality of tubes extending down from said upper partition to a level in said reaction vessel below said second partition, a second plurality of tubes extendingA downwardly from said second partition to a level. in said vessel spaced a substantial distance below the lower ends of said rst named tubes, i'iuid distributors in said vessel a. substantial distance below the lower ends ofsaid' second named tubes, a "gas outlet from said vessel at a level below said lower partition and above the lower ends of said first named tubes, and anoutlet conduit for solid material connected to the lower end. oi' said reaction vessel.

4. Apparatus for conducting a chemical reaction comprising in combination, a reaction vessel, a. heating vessel having. a heating iiuid inlet `and a heating fluid outlet near its oppositeends positioned above said reaction vessel, a cooling-vessel having a cooling fluid inletand a cooling fluid outlet near its opposite ends also positioned above said reaction vessel, an upper horizontalv partition acrossv said reaction vessel spaced below the upper end thereof, a second horizontal partition across said reaction vessel at a level in the upper section thereof spaced substantially below said first' partition, said partitions dividing'fsaid reaction vessel into' three superposed chambers, a conduit for solid ilow extending down from said cooling vessel to thefchamber abo'vesaid upper partition in said reaction vessel, a conduit extending down from said heating vessel to a point in the upper section of the chamber betweenisai'd partitions in said reaction vessel, a steam inlet connecting into saidlast named conduit at an intermediate point along its length, a plurality of tubes. for solid `flow extending fromthe upper face of said upper partition to) points in said reaction vessel shortly below said lower partition, a plurality of tubes for solid ow extending from the upper surface of said lower partition to points in said reaction vessel spaced a substantial vertical distance below the lower ends of said first named tubes, fluid distributors in said reaction vessel spaced a substantial distance below the lower ends of said second named tubes, conduit means to supply fluid to said distributors, a gas outlet on said vessel at a level between said lower partition and the lower ends of said first named tubes, an outlet conduit for solid Withdrawal connected to the lower section of said reaction vessel, a conveyor for transferring solid material from said outlet conduit to a discharge at a level above said heater and cooler and conduits communicating the conveyor discharge with the upper sections of both the heater and the cooler.

5. Apparatus for conducting a chemical reaction comprising in combination, a reaction vessel, a heating vessel having a heating fluid inlet and a heating fluid outlet near its opposite ends positioned above said reaction vessel, a cooling vessel having a cooling fluid inlet and a cooling fluid outlet near its opposite ends also positioned above said reaction vessel, an upper horizontal partition across said reaction vessel spaced below the upper end thereof, a second horizontal partition across said reaction vessel at a level in the upper section thereof spaced substantially below said first partition, said partitions dividing said reaction vessel into three superposed chambers, a conduit for solid now extending down from said cooling vessel to the chamber above said upper partition in said reaction vessel, a conduit extending down from said heating vessel to a point in the upper section of the chamber between said .partitions in said reaction vessel, a steam inlet connecting into said last named conduit at an intermediate point along its length, a plurality of tubes for solid ow extending from the upper face of said upper partition to points in said reaction vessel shortly below said lower partition, a plurality of tubes for solid flow extending from 'the upper surface of said lower partition to points in said reaction vessel spaced a substantial vertical distance below the lower ends of said rst named tubes, flared skirts having orices therethrough on the lower ends of said last named tubes, uid distributors in saidv reaction vessel spaced ia substantial distance below the lower ends of said second named tubes, conduit means l `to supply fluid to said distributors, a gas outlet l .on said vessel at a level between said lower partition and the lower ends of said rst named tubes, an outlet conduit for solid withdrawal connected to the lower section of said reaction vessel, a conveyor for transferring solid material from said outlet conduit to a discharge at a level above said heater and cooler and conduits communifzontally across the upper section of said vessel a short distance below its upper end, a second partition extending horizontally across said vessel at an intermediate level spaced a substantial distance below said rst partition and a substantial distance above the lower end of said Vessel, said partitions dividing said vessel into three superposed chambers, an inlet conduit for solid material extending through the top of said vessel and 'terminating at a level spaced above said first partition a plurality of tubes for solid flow ex.- tending downwardly from said rst partition an terminating shortly below said rst partition a substantial distance above said second partition, a second plurality of tubes for solid flow extending downwardly from said rst named partition and through said second named partition to terminate at a level shortly below said second named partition, a plurality of tubes for solid flow extending downwardly from said second partition and terminating on their lower ends a substantial distance below the lower ends of said second named tubes but above the lower end of said vessel, a plurality of gas distributors in the lwer section of said vessel at a level spaced a substantial distance below the lower ends of said last named tubes, conduit means to supply gas to said distributors, a gas outlet on said vessel at a level below said second partition but above the lower ends of said second named tubes, separate gas distributors positioned in said vessel at a level shortly above said second partition, conduit means to supply gas to said distributors, av gas outlet on said vessel at a level below said upper partition but above the lower ends of said rst named tubes and an outlet conduit for solid withdrawal on the lower end of said vessel.

SYLVANDER C. EASTWOOD. ROBERT D. DREW.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS` Number Name Date 2,416,214 Payne Feb. 18, 1947 2,421,840 Lechthaler June 10. 1947 

1. APPRATUS FOR CONDUCTING A CHEMICAL REACTION COMPRISING IN COMBINATION, A REACTION VESSEL, A HEATER FOR SOLID GRANULAR MATERIAL, A COOLER FOR SOLID GRANULAR MATERIAL, AN UPPER HORIZONTAL PARTITION ACROSS SAID REACTION VESSEL SPACED BELOW THE UPPER END THEREOF, A SECOND HORIZONTAL PARTITION ACROSS SAID REACTION VESSEL SPACED SUBSTANTIALLY BELOW SAID FIRST PARTITION AND A SUBSTANTIAL DISTANCE ABOVER THE LOWER END OF SAID VESSEL, SAID PARTITIONS DIVIDING SAID REACTION VESSEL INTO THREE SUPERPOSED CHAMBERS, A CONFINED PASSAGE FOR SOLID MATERIAL TRANSFER COMMUNICATING SAID COOLER WITH THE CHAMBER ABOVE SAID UPPER PARTITION, A CONFINED PASSAGE FOR SOLID MATERIAL TRANSFER COMMUNICATING SAID HEATER WITH THE CHAMBER BETWEEN SAID PARTITIONS, A PLURALITY OF TUBES EXTENDING DOWN FROM SAID UPPER PARTITION TO A LEVEL IN SAID REACTION VESESL BELOW SAID SECOND PARTITION, A SECOND PLURALITY OF TUBES EXTENDING DOWNWARDLY FROM SAID SECOND PARTITION TO A LEVEL IN SAID VESSEL SPACED A SUBSTANTIAL DISTANCE BELOW THE LOWER ENDS OF SAID FIRST NAMED TUBES, FLUID DISTRIBUTORS IN SAID VESSEL A SUBSTANTIAL DISTANCE BELOW THE LOWER ENDS OF SAID SECOND NAMED TUBES, A GAS OUTLET FROM SAID VESSEL AT A LEVEL BELOW SAID LOWER PARTITION AND ABOVE THE LOWER ENDS OF SAID FIRST NAMED TUBES, AND AN OUTLET CONDUIT FOR SOLID MATERIAL CONNECTED TO THE LOWER END OF SAID REACTION VESSEL. 